Two-stage alkylation process



July 25, 1944.5

B. HOPPER TWO-STAGE AALK'I'1'.|I\.T]1ON PROCESS Filed June '20, 1939 Baszl Hopper BY g ATTORNEY.

Patented July 25, 1944 UNITED sTATEs PATENT oFr-lcE TWO-STAGE ALKYLAT'ION PROCESS Basil Hopper, Palos Verdes Estates, Calif., asslgnor to Union Oil Company of California, Los Angeles, Calif., a corporation of California Application June zo, 1939, sem1Nn.zso,1z1 l 4 claims. (ci. zso-sss.4

This invention relates to a process for the production of alkylated hydrocarbons from hydrocarbon fractions containing oleflns and fractions containing isoparafiins.

e., alkylation and polymerization.

lected which will produce maximum alkylation and a minimum amount of polymerization providing it is desired to :produce the side chain In can'ying out the alkylation of isoparamns with olens it is desirable at all times to have a high ratio'of isoparaiiins to olefins since the 'ratio between these two reacting components governs to a large degree the polymerization of the oleilns. It is, therefore, desirable .to employ a ratio of at least ten parts of isoparailin to one part of the olefin and preferably a ratio in the order of fifty to one or one hundred to one.

In carrying out the alkylation of isoparaillns with olei'lns it is also desirable to employ sulphuric acid having an H2SO4 concentration between 95% and 100%. However, I may employ sulphuric acid having an actual H2504 concentration as low as 92%. Below this latter concentration the sulphuricacid ceases to be 'an eilicient alkylation catalyst and begins to favor tl'ie polymerization of olefins.

In the alkylation .of butylene with isobutane it is desirable to employ a temperature between 30 F. and 60 F. and preferably in the order of 55 F. Furthermore, it is desirable to maintain sumcient pressure on the reactants to maintain appreciable alkylation takes place lbetween propylene and the isoparaiiin (isobutane or isopentane); the propylene to alarge extent simply passes into solution in the'sulphuric acid.

Where a mixed olen fraction containing, as

for example, propylene and Ibutylene is alkylated ence of a catalyst such as sulphuric acid having an H2804 concentration between 95% and 100% I prefer to proceed as follows:

'Ihe olefin stock containing the butylene and propylene is mixed with an isoparafn such as,

isobutane in the proportion of at least ten parts of the isobutane to one part of the olefin stock. This mixture is then contacted with sulfuric acid having an H1504 concentration between 95% and 100% and at a temperature between 30 F. and F. At this temperature the butylene reacts with the isobutane to produce alkylated hydrocarbons but there is no appreciable reaction between the propylene and the isobutane. A large portion of the propylene passes into solution in the sulphuric acid.

After the initial contact oetween the sulphuric acid and the isobutane mixed with butylene and propylene this mixture is passed into a settling chamber and the acid phase is separated from the alkylated products and unreacted gases. The acid phase containing the dissolved propylene is heated to increase its temperature at a point in the range between F. and 100 F. and preferably around F. and at this temperature the sulphuric acid containing the dissolved propylene is contacted with a further quantity of the isobutane or other isoparaflin which reacts with the olefin dissolved in the sulphuric acid to form a further quantity of alkylated hydrocarbon. 'I'his mixture then passes to another settling chamber where the alkylated hydrocarbon and unreacted gases are separated from the sulphuric acid. Providing this acid has not'dropped to an HzSO4 concentration below 92% it may be y used again either in the first or second stag of the process for further 'alkylatlom The object of the invention, therefore, resides in contacting a series of olefins, preferably propylene and butylene mixed with an isoparamn, such as isobutane, with sulphuric acid having an H2804 concentration between 92% and 100% and preferably 96% at a temperature at which one of the oleflns reacts with the isoparafn to form an alkylated hydrocarbon and at which temperature another olefin of the series doesv not react to any appreciable extent with the isoparailin but simply passes into solution in thesulphuric acid, then recovering the sulphuric acid containingv the dissolved olen, increasing the temperature of this acid to a point at which the dissolved olefin will react with an isoparaflin, such as isobutane, and then contacting the sulwith an iswraflinl such as isobutane in the pres- 55 phuric acid with the isoparaflin.

Other objects will appear from the disclosure in connection with the flow diagram.

As explained above it is desirable to employ suiilcient pressure in each stage -of the processto maintain the reacting hydrocarbons in a liquid state.

The olefin stock which I prefer to use may' consist pf a mixture of gases containing olen molecules .of more than two carbon atoms and less than thirteen carbon atoms or it mayA consist of polymerized olenns produced by contacting gaseous olenns with phosphoric or sulphuric acid or it may contain both gaseous and polymerized oleflns. Preferably I wish to employ olefin fractions containing propylene and butylene. As isoparain stock I prefer to use isobutane or isopentane or a mixture of these isoparamns.

Referring to the drawing, olefin stock is introduced into the system through line I, isoparafiin stock is introduced through line 2. Pump 3 then passes the mixture of olefin and isoparaflin stock together with acid introduced through line I3 into mixer 4 where the mixture of olefin,

isoparafiin and acid is thoroughly mixed. This mixture then passes into settler 5 which is maintained in the order of F. to 60 F. From the top of settler 5 the alkylated hydrocarbons andunreacted oleflns and isoparaiilns are with'- drawn, a portion of this mixture may be recycled to mixer 4 through line 1 and another portion of this material may be continuously withdrawn through line 1.

The acid phase in settler 5 is withdrawn from the bottom of this settler and passed by -means of pump 6 through heatI exchanger II and heater I0 and through lin'e 9 tov mixer I8 where it is thoroughly mixed with unreacted isoparaiiins withdrawn fromsettler 5 which are introduced through line 1 and pump 0 into mixer I8. The temperature of the materials in mixer I8 is preferably maintained within the range of 70 F.

to 100 F. The materials in mixer I8,'after thori ough mixing, are passed into settler I4 where the alkylated products together with the unreacted t gases are separated from the acid phase. A portion of the alkylated products and unreacted gases may be returned to mixer I8 through line I0 and another portion of this material may be withdrawn through line 20 and passed to the fractionating tower for the separating of the alkylated hydrocarbons from the unreacted gases.

The acid phase withdrawn from settler I4, through line I5 passes by means of pump I6 through line I1 and interchanger Il and cooler I2 backto line I3 where it is used in the first alkylation stage. Fresh acid may be introducedA into the system through line v2I and vspent acid may be withdrawn throughline v22.

As explained above, the mixture of propylene and butylene is contacted with isoparaflln in mixer 4 at a temperature between 30 F. and 60 F. This contact causes va reaction to take place between the butylene and the isoparaflln but the major portion of propylene remains dissolved in the acid phase at this temperature. The acid phase i'n settler 5 is withdrawn, as explained above, through line 9 and after its temperature has been raised to a point between '70 F. and 100 F. it is contacted with isoparaiiln in mixer Il. At this temperature the propylene dissolved in the sulphuric acid reacts with the isoparaflin to form alkylated hydrocarbons' which are withyield of alkylated hydrocarbons than can be obtained providing the mixture of olens are mixed with the isoparaihn and then contacted with the sulphuric acid catalyst at one temperature.

` It is, therefore, an object of the present invention to contact amixture of olefins with sulphuric acid and isoparafiins at a temperature wherein one of the oleflns reacts with isoparaflins to form alkylated hydrocarbons and the major portion of the other olens remains in a dissolved `state in the sulphuric acid, to separate the acid solution of the unreacted oleiins from the alkylated hydrocarbons and after raising its temperature to a point wherein it readily reacts with an isoparafhn, thereafter contacting the heated acid containing the dissolved olefin with an isoparaflln to form a further quantity of alkylated hydrocarbons.

As a further modification of the process the isoparafiin may be mixed with the acid phase withdrawn from the feed stage containing the dissolved olefin and this mixture may then be heated until it reaches a temperature at which the olefin will react with the isoparafdn.

My method of alkylation is also applicable to processes in which the unsaturated hydrocarbon stock employed is predominately composed of single oleflns, such as for example,propylene or butylene. To illustrate, if butylene and isobutanel are contacted with sulphuric acid of 92% to 100% concentration at a temperature between 30 F. and 60 F. and preferably around 55 F. and preferably under suflicient pressure to mantaln the reacting hydrocarbons in a liquid state I nd that a certain amount of butylene dissolves in the sulphuric acid. If the acid phase' containing-the dissolved butylene is contacted with isobutane within the temperature range between 30 F. and` 60 F. and preferably around 55 F. and preferably under sulcient pressure to maintain the isobutane in a liquid state it is possible to react a substantial portion of the dissolved butylene with the isopar. afiin and thereby form additional alkylated hydrocarbons. Furthermore, where a fraction rich in propylene has been mixed with an isopar-v ailn and contacted with sulphuric acid having a concentration between 92% and 100% H2804 the same phenomena occurs as in the `case' of the butylene, set forth above. Between the temperatures of '10 F. and 100 F. a greater proportion of the propylene tends to react with the isoparaln to form alkylated hydrocarbons, however, the reaction is not complete and some of the propylene remains dissolvedin the acid. This dissolved propylene may be converted into alkylated hydrocarbons by contacting the sulphuric acid with an isoparailln, such as isobutane.

The foregoing description is not to be taken as limiting, but only illustrative of my invention' as many variations may be made by anyone skilled in the art coming within the scope of the following claims.

l. A process for the production of' alkylated hydrocarbons which comprises reacting an isoparafEIn withi an olefin in the presence of concentrated sulphuric acid thereby forming alkylated hydrccarbons and dissolving a portion oi' therolefin in the sulphuric acid, separating the hydrocarbon phase containing unreacted isodrawn, as explained above, through lines I9 and Y By this method I am able to produce a greater paraffin in admixture with said alkylated hydrocarbons from the sulphuric acid phase containing the dissolved olefin, recycling a portion of said hydrocarbon phase to said stage, and con- `tacting said acid phase containing the dissolved oleiin with said hydrocarbon phase at a temperature higher than that employed during the initial .contacting step of the isoparaflin, oleiins and acid and thereby forming additional allnrlated hydrocarbons.

2. A process ior the -production of alkylated hydrocarbons which comprises mixing an oleiinic hydrocarbon fraction containing propylene and butylenes with an isoparamnic hydrocarbon fraction containing isobutane, alkylating the butyl'- enes in said mixture in one stage of the process by contacting the mixture with concentrated sul furic acid at a temperature between 30 F. and 60 F., separating the resulting acic. phase containing dissolved unreacted propylene from the resulting hydrocarbon phase containing -unreacted isobutane -and alkylated hydrocarbons, recirculating a portion oi said hydrocarbon phase to said stage, and mixing the remainder of said hydrocarbon phase with said acid phase in a subrsequent stage at a temperature between 70 F.

and 100 F. so as to alkylate said propylene dissolved therein.

arating the resulting acid phase containing dissolved unreacted oleflns from the resulting hydrocarbon phase containing unreacted isoparamn and alkylated hydrocarbons, recirculating a portion of said hydrocarbon phase to said stage,

and mixing the remainder of said hydrocarbon phase with said acid phase in a subsequent stage at a temperature higher than that employed in the Aaforesaid stage so as to alkylate said oleiins dissolved thereinn 4. A process for the production of allmlated hydrocarbons which comprises mixing an oieiinic hydrocarbon fraction with an isoparailinic hydrocarbon, alkylating a portion oi the olens in said mixture in one stage oi the process by contacting the mixture with concentrated sulfuric acid, separating the resulting acid phase containing dissolved unreactedolens from the resulting hydrocarbon phase Ycontaining unreacted isoparamn and alkylated hydrocarbons, recirculating a portion of said hydrocarbon phase to said stage. and mixing an isoparain ymixture comprising another portion ot said hydrocarbon 3. A process for the production of alkylated 25 hydrocarbons which comprises mixing an oleiinlc hydrocarbon fraction with an isoparaflinic hydro'- carbcn. alkylating a portion of the olens in said mixture in one stage of the process by contacting the mixture with concentrated sulfuric acid, sep- 30 phase with said acid phase in a subsequent stage at a temperature higher than that employed in the aforesaid stage so as to aikylate said oleilns dissolved therein. v

B ASIL HOPPIER. 

